Process for the manufacture of unsaturated nitriles from olefins and ammonia



1967 J. CALLAHAN ETAL 3,354,197

PROCESS FOR THE MANUFACTURE OF UNSATURATED NITRILES FROM OLEFINS AND AMMONIA Original Filed April 25, 1962 3 Sheets-Sheet 1 40 M KEY PERCENT CONVENSION TO ACRYLONiTRILE Bose Coiolyst-Conirol A 30* Bi-Promoted Catalyst-Conirol B -Bi a B-Promoted Cc'olysi of ExornpleI F/G, TEMPERATURE, F

Bose Cotol st-Conirol A BiPromo1ed Catalyst-Control B -BiGB-Pmrfiotad Catalyst of ExomplelI PERCENT CONVENSION TO ACRYLONITRILE TEMPERATURE, "F

NOW 1957 J. L. CALLAHAN ETAL 3,354,1g7

PROCESS FOR THE MANUFACTURE OF UNSATURATED NITRILES FRQM OLEFINS AND AMMONIA. 7 Original Filed April 25, 1962 a Sheets-Sheet 2 Bi- Mn-B-Promoied Goinlysi of Example-21H 5O 40 PERCENT CONVENSION TO ACRYLONITRILE 850 875 900 925 950 TEMPERATURE, F.

80 UJ *5 70 2 O u.- 25 5 5 6O 4 g 0 w I'- C!) z w Q o: 2 5 40 LU CC E 0 .2 3O F- Z '6' a: 20 LIJ D.

I 2 3 4 5 6 7 8 9 IO WT. PERCENT Bl ON 0.5% B-GONTAINING CATALYST J. CALLAHAN ETAL 3,354,197 PROCESS FOR THE MANUFACTURE OF UNSATURATED NITRILES FROM OLEFINS AND AMMONIA Original Filed April 25. 1962 Nov. 21, 1967 5 Sheets-Sheet 5 O O o O O 8 7 6 w 4 3 WT. /o B ON 5% Bl-CONTAINING CATALYST-A United States latent O 3 354,197 PROCEES FOR THE MANUFACTURE OF UN- SATURATED NITRELES FROM OLEFTNS AND AMMONEA James Louis (Iailalran, Redford, Berthold Gertisser, Cleveland Heights, and Joseph J. Szaho, Chagrin Falls, Ohio, assignors to The Standard Oil Company, Cleveland, Ohio, a corporation of Ohio Original application Apr. 25, 1962, Ser. No. 190,038, now Patent No. 3,248,340, dated Apr. 26, 1966. Divided and this application Aug. 9, 1965, Ser. No. 510,414

6 Claims. (Cl. 260-4653) This is a division of application Ser. No. 190,038, filed April 25, 1962, now US. Patent 3,248,340.

This invention relates to the oxidation of olefin-ammonia mixtures to unsaturated nitriles, such as propyleneammonia to acrylonitrile, using an improved oxidation catalyst consisting essentially of oxides of the elements bismuth and molybdenum, and optionally, phosphorus, promoted by oxides of boron and bismuth.

The Callahan, Foreman and Veatch US. Pat. No. 2,941,007 describes the oxidation of an olefin such as propylene and the various butenes with oxygen and a solid catalyst composed of the oxides of bismuth, molybdenum and silicon, and optionally, phosphorus. This catalyst selectively converts propylene to acrolein, isobutylene to methacrolein, aand ,G-butylene to methyl vinyl ketone and to butadiene, etc. High yields are obtainable, although in the case of the butenes, careful control of reaction conditions may be required in order to direct the reaction in favor of either methyl vinyl ketone or butadiene, depending upon which of these alternative products is desired.

The Idol, Jr., Patent No. 2,904,580, employs the same catalyst to convert propylene, ammonia and oxygen to acrylonitrile, at approximately atmospheric pressures and elevated temperatures. Excellent conversions, usually in the range of 40 to 80%, nitrogen basis, of useful products are obtainable.

The catalyst In accordance with the instant invention, the catalytic activity of such bismuth oxide-molybdenum oxide catalysts is greatly enhanced or promoted by the combination therewith of a mixture of boron and additional bismuth in the form of their oxides, referred to hereinafter as promoters. The promoters in accordance with the invention are best applied by impregnation or surface coating of the catalyst, after its formation in accordance with the procedure described in Ser. No. 851,919, the disclosure of which is hereby incorporated by reference. Further, in accordance with the invention, it has been determined that a portion of the supplemental bismuth oxide promoter can be replaced with manganese oxide, and that phosphorus oxide can also be present as a supplemental oxide.

The proportions of boron oxide and bismuth oxide, with or without phosphorus oxide and/or manganese oxide, are important in obtaining the optimum enhanced activity. The boron oxide concentration, calculated as boron, should be within the range from about 0.5 to about 1% by weight; and the amount of bismuth oxide, calculated as bismuth, should be within the range from about to about 10% by weight, although more than 10% can be used, if desired. If manganese oxide is employed, it can be used on a bismuth oxide equivalent Weight basis, but not more than about one third of the promoter bismuth oxide, calculated as bismuth, can be replaced by manganese oxide.

While the catalyst of this invention may be employed without any support, it is desirable to combine it with a support. A preferred support is silica because the silica improves the catalytic activity of the catalyst. The silica 3,354,197 Patented Nov. 21, 1967 may be present in any amount but it is preferred that the catalyst contain between about 25 to by weight of silica. Many other materials such as alundum, silicon carbide, alumina-silica, alumina, titania and other chemically inert materials may be employed as a support which will withstand the conditions of the process.

The catalyst may comprise phosphorus, also present in the form of the oxide. Phosphorus will affect, to some extent, the catalytic properties of the composition, but the presence or absence of phosphorus has no appreciable effect on the physical properties of the catalyst. Thus, the composition can include from 0%, and preferably from at least 0.1%, up to about 5% by weight of phosphorus oxide, calculated as phosphorus.

The promoter is incorporated with the catalyst base by impregnation thereof, using an aqueous solution, dispersion, or suspension of a boron compound and of a bismuth compound, with or without a manganese compound, either the oxide, or a compound thermally decomposable in situ to the corresponding boron oxide, bismuth oxide, and manganese oxide, respectively, without formation of other deleterious metal oxide residue, for instance, ammonium phosphate, ammonium tetraborate, ammonium permanganate, manganese nitrate, bismuth nitrate, boric acid, bismuth hydroxide, manganese hydroxide, bismuth phosphate, and bismuth borate. The phosphorus-containing compounds also add phosphorus to the catalyst. After impregnation with such solution, employed in a concentration and amount to provide the desired amount of bismuth and boron, and optionally, manganese, the catalyst base is dried, and then calcined at a temperature above that at which the compounds applied are decomposed to the oxides. Temperatures in excess of 800 F. but below that at which the catalyst is deleteriously aifected, usually not in excess of about 1050 F., can be used.

The basic catalyst composition comprises bismuth oxide and molybdenum oxide, the bismuth-to-molybdenum ratio BizMo being controlled so that it is at all times above 1:3. There is no critical upper limit on the amount of bismuth, but in view of the relatively high cost of bismuth and the lack of an improved catalytic efiiect when large amounts are used, generally the atomic ratio bisinuth to molybdenum BizMo of about 3:1 is not exceeded. The nature of the chemical compounds which compose the basic catalyst is not known. The catalyst may be a mere mixture of bismuth and molybdenum oxides, with or without phosphorus oxide, but it seems more likely that the catalyst is a homogeneous micro mixture of loose chemical combinations of oxides of bismuth and molybdenum, with, optionally, phosphorus, and it is these combinations which appear to impart the desirable catalytic properties to this catalytic composition. The catalyst can be referred to as bismuth molybdate, or, when phosphorus is present, as bismuth phosphomolybdate, but this term is not to be construed as meaning that the catalyst is composed of these compounds.

The bismuth and boron, and optionally, manganese, compounds added thereto as promoters may or may not enter into the chemical composition of the catalyst. Bismuth added later with boron produces a different result from boron added to a catalyst composition containing more than the usual amount of bismuth, i.e., that stoichiometrically equivalent to the weight of added boron, and has a different function, since the enhanced catalytic effect is not obtained when boron oxide is combined with a composition previously containing the same excess of bismuth. Hence, the promoted catalytic effect may be due to some complex boron oxide-bismuth oxide combination formed on the surface of the catalyst. In any event, the boron and bismuth are present in the form of their oxides, when combined therewith later in accordance with the invention.

The bismuth molybdate catalyst composition of the invention may have the following composition ranges, as long as the atomic ratio of bismuth to molybdenum is above 1:3:

Element: Weight, percent Bismuth Z9.8478.08 Molybdenum 11.32-47.29 Oxygen 9.96-26.84 Phosphorus -2.40

This same composition may be expressed in the form of the following empirical formula:

Bl P MOuO where a is 4 to 36, b is 0 to 2, and c is /2 n-a-l-Vz n-b-l- /z p-12 where a, b and c are as defined above.

When the silica is present as about 30 to 70 weight percent of the final composition, the empirical formula is a b 12 c'( 2)30 to 150 where a, b and c are as defined above.

To this are to be added bismuth oxide and boron oxides, as such or as formed in situ from other added bismuth and boron compounds, so that the empirical formula of the promoted catalyst in accordance with the invention corresponds to the followin z 85-93% a b IZ c'( 2)0-600) The values of a, b and c are in accordance with the definitions given above.

When the atomic ratio of bismuth to molybdenum BizMo is about 3 :4, the empirical formula is (5) 8593% s b iz e'( 2)0-so0)' 5.5-11.5% Bi 0 -1.5 3.5% B203 The values of b and c are as defined above.

When the silica is present as about to 70 weight percent of the final composition, the empirical formula is Where a, b and c are as defined above.

Oxidation of olefins t0 niir1'le.rThe reactants The reactants used are an olefin or mixture thereof, and oxygen, plus ammonia.

By the term olefin, as used herein and in the appended claims, is meant the open-chain as well as cyclic olefins. Among the many olefinic compounds which may be utilized in accordance with the process of the invention, the following compounds are illustrative: propylene, butcne-l, butene-2, isobutylene, pentencl, pentene-Z, 3-methyl-butene-l, Z-methyl-butene-Z, hexene-l, hcxene- 2, 4-rnethyl pentene-l, 3,3-dimethyl-butenel, 4-'ncthylpentene-Z, octene-l, cyclopentene, cyclohexcne, 3-methylcyclohexene, etc.

This invention is directed particularly to the oxidation of the lower alkenes (3 to 8 carbon atoms) but higher alkenes may also be utilized ulth et'ticacy. These compounds and their various homologs and anaogs may be substituted in the nucleus and/ or in the substituents in various degrees by straight-chain alicyc ic or heterocyclic radicals. The process of the invention is applicable to 41- individual olefins as vie l as to mixtures of olcfins and also to mixtures of olefins with the corresponding or other saturated organic compounds.

The process of this invention is particularly adapted to the conversion of propylene to acryionitrile. In its preferred aspect the process comprises contacting a mixture comprising propylene, ammonia and oxygen with the catalyst at an elevated temperature and at atmospheric or near atmospheric pressure.

Any source of oxygen may be employed in this process. For economic reasons, however, it is preferred that air be employed as the source of oxygen. From a purely technical viewpoint, relatively pure molecular oxygen will give equivalent result The molar raLio of oxygen to the olefin in the feed to the reaction vessel should be in the range of 0.521 to 3:1 and a ratio of about 1:1 to 2:1 is preferrc The presence of the corresponding saturated hydrocarbon does not appear to influence the reaction to any appreciable degree, and these materials appear to act only as diluents. Consequently, the presence of the correspon-c'ing saturated hydrocarbons or other saturated hydrocarbons in the feed to the reaction is contemplated within the scope of this invention. Likewise, other diluents such as nitrogen and the oxides of carbon may be present in the reaction mixture without deleterious effect.

Ammonia-olefin ratio The molar ratio of ammonia to olefin in the feed to the reaction may vary between about 0.05:1 to 511. There is no real upper limit for the ammonia-olefin ratio, but there is generally no point in exceeding the 5:1 ratio. At ammonia-olefin ratios appreciably less than the stoichiometric ratio of 1:1, various amounts of oxygenated derivatives of the olefin will be formed.

Significant amounts of unsaturated aldehyde or ketone as well as nitrile will be obtained at ammonia-olefin ratios substantially below 1:1, i.e., in the range of 0.15:1 to 0.75:1. Outside the upper limit of this range only insignificant amounts of aldehyde or ketone will be produced, and only very small amounts of nitrile will be produced at ammonia-olefin ratios below the lower limit of this range. It is fortuitous that within the ammoniaolefin range stated, maximum utilization of ammonia is obtained and this is highly desirable. It is generally possible to recycle the olefin to the process, whereas the unconverted ammonia may be recovered and recycled only with diificulty.

H O-olefin ratio A particularly surprising aspect of this invention is the etfect of water on the course of the reaction. We have found that the presence of water in the mixture fed to the reaction vessel improves the selectivity and yield of the reaction as far as the production of the nitrile is concerned. Improvements on the order of several hundred percent have been observed in the presence of water as compared to similar runs made in the absence of added water. Consequently, the presence of water has a marked beneficial effect on this reaction, but reactions not including water in the feed are not to be excluded from this invention.

In general. the molar ratio of Water to olefin should be at least about 0.25:1. Ratios on the order of 1:1 are particularly desirable but higher ratios may be employed, i.e., up to about 10:1. Because of the recovery problems involved, it is generally preferred to use only so much wate as is necessary to obtain the desired improvement in yield. It is to be understood that water does not behave as an inert diluent in the reaction mixture. This conclusion has been verified by employing other diluents in the reaction mixture, such as propane and nitrogen. No corresponding improvement in yield and selectivity is observed with such diluents. Although the exact manner in which the '-.-.a.cr affects the reaction is not understood, it is clear that the water does have a significant influence on the reaction.

One theory which has been postulated to explain the effect of water on the reaction involves the phenomena occurring at the surface of the catalyst. Water, because of its polarity, may assist in the desorption of the reaction products from the surface of the catalyst. According to another hypothesis, the water may change the nature of the catalyst at the catalyst surface by affecting the acidity of the catalyst. Notwithstanding the fact that either of these theories may be in error, the improved results occasioned by the use of water are evident and the theory by which these results are to be explained is therefore to be considered immaterial.

Process conditions The temperature at which the reaction is carried out may be any temperature in the range of from about 550 to about 1000 F. The preferred temperature range runs from about 800 to 950 F.

The pressure at which the reaction is conducted is also an important variable, and the reaction should be carried out at about atmospheric or slightly above atmospheric (2 to 3 atmospheres) pressure. In general, high pressures, i.e., above 250 p.s.i.g., are not suitable for the process since higher pressures tend to favor the formation of undesirable by-products.

The apparent contact time employed in the process is not especially critical, and contact times in the range of from 0.1 to about 50 seconds may be employed. The apparent contact time may be defined as the length of time in seconds which a unit volume of gas measured under the conditions of reaction is in contact with the apparent unit volume of the catalyst. It may be calculated, for example, from the apparent volume of the catalyst bed, the average temperature of the reactor, and the fiow rates in the vessel of the components of the reaction mixture. The optimum contact time will, of course, vary depending upon the olefin being treated, but in general it may be said that a contact time of from 1 to seconds is preferred.

In general, any apparatus of the type suitable for carrying out oxidation reactions in the vapor phase may be employed in the execution of this process. The process may be conducted either continuously or intermittently. The catalyst bed may be a fixed bed employing a pelleted catalyst or, in the alternative, a so-called fluidized bed of catalyst may be employed. The fluidized bed offers definite advantages with regard to process control in that such a bed permits closer control of the temperature of the reaction as is Well known to those skilled in the art.

The reactor may be brought to the reaction temperature before or after the introduction of the reaction feed mixture. However, on a large scale operation it is preferred to carry out the process in a continuous manner, and in such a system the recirculation of the unreacted olefin is contemplated. Periodic regeneration or reactivation of the catalyst i also contemplated, and this may be accomplished, for example, by contacting the catalyst with air at an elevated temperature.

The products of the reaction may be recovered by any of the methods known to those skilled in the art. One such method involves scrubbing the eflluent gases from the reactor with cold water or an appropriate solvent to remove the products of the reaction. In such a case, the ultimate recovery of the products may be accomplished by conventional means. The efiiciency of the scrubbing operation may be improved when water is employed as the scrubbing agent by adding a suitable wetting agent to the water. Where molecular oxygen is employed as the oxidizing agent in this process, the resulting product mixture remaining after the removal of the nitriles may be treated to remove carbon dioxide with the remainder of the mixture containing the unreacted propylene and oxygen being recycled through the reactor. In the case where air is employed as the oxidizing agent in lieu of molecular oxygen,-

the residual product after separation of the nitriles and other carbonyl products may be scrubbed with a n0npolar solvent, e.g., a hydrocarbon fraction, in order to recover unreacted propylene and in this case the remaining gases may be discarded. The addition of a suitable inhibitor to prevent polymerization of the unsaturated products during the recovery steps is also contemplated.

The following examples, in the opinion of the inventors, represent preferred embodiments of their invention:

Example 1 A bismuth silicophosphomolybdate catalyst base was prepared by the following procedure:

74 g. of an 85% phosphoric acid was added to 8330 g. of an aqueous silica sol containing silica. Next, 2800 g. of bismuth nitrate was dissolved in a solution made by diluting 160 ml. of 70% nitric acid to 1540 ml. with distilled Water. The bismuth nitrate solution was then added to the silica sol. Next, 1360 g. of ammonium molybdate was dissolved in 1540 ml. of distilled water, and this solution added to the silica sol. The resulting catalyst slurry was dried in an oven at 200 F. for 24 hours and then calcined in a furnace at 800 F. for 24 hours. After cool ing, the catalyst was ground into particles, and screened through a 10 mesh screen. A portion of the 8-10 mesh material was then made into tablets, while the remainder was retained for use as a control, designated hereinafter as Control A.

The final catalyst composition corresponded to the empirical formula Bi PMo O (SiO having the following composition:

This tabletted catalyst was then impregnated with promoters in accordance with the invention, by the following procedure:

81.8 g. of boric acid was dissolved in hot water and diluted up to 420 ml. This hot solution was used to impregnate 400 g. of the tabletted catalyst prepared as described above, dipping tablets of the catalyst contained in a wire basket in the boric acid solution for 4 minutes, then removing and draining them for 4 minutes. By this procedure, 120 ml. of the boric acid solution was absorbed by the catalyst, equivalent to 23 g. H BO The wet catalyst was dried overnight, and a portion was set aside, for use later as Control C.

The remainder of the boric-acid impregnated catalyst wa mixed well with a solution prepared by dissolving 47 g. of bismuth nitrate Bi(NO -5H O in 40 cc. of concentrated nitric acid, specific gravity 1.42, diluting to 120 cc. with water. Another portion of the base catalyst (Control A), not previously impregnated with boric acid solution, was then impregnated with bismuth nitrate solution in the same way. This was marked Control B. Again, the catalyst was dried at 120 C. overnight.

Controls B and C and the twice impregnated catalyst of the invention then were calcined in air for 14 to 16 hours at 800 F. Finally, the three calcined catalysts Were ground and screened, to obtain a size fraction in the 8 to 10 mesh range.

Thus, Control B contained 5% added bismuth, Control C 1% boron, Control A neither, and the catalyst of the invention, 5% added bismuth and 1% added boron together.

The promoted catalyst and the control catalysts A, B, and C without promoters and with only one promoter were employed in a series of experiments, to determine catalytic effectiveness, using a fixed bed reactor, in the oxidative conversion of propylene and ammonia to acrylonitrile. A ml. catalyst charge was used in each run. Gases 7 were metered by rotameter, and water was fed by a Sigma motor pump. The feed ratios were held constant at I-I C-CHCH /NH /Air/N /I-l O 1/1.5/ 12/4/03, and the contact time was held constant at 5 seconds. The reaction temperature was varied from 860 to 950 F. in the 8 Example II The bismuth silicophosphomolybdate catalyst of Example l was employed to prepare another series of promoted catalysts corresponding to those of Example I but series of runs Carried out The percent conversion to 9 with a lesser amount of boron. Control A, as before, was the base catalyst. Control C was prepared in the same ficrylommle versus reaction temperamle for each Catalyst Way, but using a boric acid solution containing only 40.9 15 shown In FIGUIOQE the opnmum temperature g. of boric acid. half the previous concentration, thus givrange of 865 3 of tha propylellefeed i ing a catalyst containing only 0.5% added boron, instead converted. bemg conyerted to acrylommle w 10 of 1%. Control B was identical to Example I, and the to acetonitrile, and the remainder to a mixture of carbon Catalyst of the invention contained 0 5% added boron dioxide and hydrogen cyanide. The useful yield was and5% added bismuth asthe Oxides 896% The catal sts were used in the conversion of lropylene In Contrast cqntrol the base catalyst l and ammonia to acrylonitrile, using the reactor and reacmoters at the Optlmum temperature of 860T870 gave tion conditions of Example I. The results obtained appear a total conversion of 93.2%, of which 63.4% was acryin FIGURE 2 graphing the Dercent conversion of prom/L lonitrile, 13% acetonitrile and the remainder, carbon ene to acrylonitrile agahllst tehmcratum dioxide and Pydrogen cyanide The useful .yleld was The catalyst of the inventioh at the optimum tempera- 78.6%. The Bi-promoted Control B at the optimum temture of 850M860s R gave a total conversion of 941% perature of 860 gave a total Conversion of 855% of 90 of which 72 9% was acrylonitrile 12.7% acetonitrile which 58.7% was acrylonitrile, 9.1% acetonitrile, and the and the remainder carbon dioxide hydrogen Cyanide: remamd.er carbon dloxlde and .hydrogen cyanide The The total useful yield was 94.9%. This is to be compared useful yleld was 709% The Bl'opromoted Control C at to the base catalyst, a 63.4% conversion to acrylonitrile, th optimum tempFrature of 880 total 13.0% conversion to acetonitrile, and the remainder carcon-verslon 6f Whlch was acrylomgnle 3% acebon dioxide and hydrogen cyanide givin a total converf acrolem a the remamder carbon sion of 93 2% and a useful conver sion o? 78.6% Again 10x1 e an ro en c am e. Thus7 aloze as a poison not as a promoter Control was poisoned by the 0.5% boron, and Control bismuth alone also has a definite depressing effect on Cwas Example L maximum yield, while the two together materially enhance Example 111 iii liilfifi 35.31212? 53153.? iiiiiii lv il' an- Example I s s? using the s P s catalyst, ployed in fluidized form for the Conversion of propylene and the same bismuth nltrate and boric acid impregnatand ammonia to a l iufl The base catalyst was used ing solutions and procedure. However, the amount of as Control A. Contact time in all runs was 7.6 seconds, 3 bismuth nitrate was reduced by thereby ffidlfclllg ms and the pressure was atmospheric. The other process con- 10ml bismlllh lhfi Catalyst {0 3%, and ammonlum P ditiOns and the data obtained appear in Table I below. manganate added to the bismuth nitrate solution in an TABLE I Percent Conversion, Carbon Basis C3=/.\lI/NH3 /H2O T m p., "CU Mole Ratio r. y l m m HUN i' oful Told] Select, 1 Yield nltrile l mtrile I l 1 1 238 1: 1 n ti 3-; in 900 2:110 215 l 313 9.13 1 l 333 ii-1 l 214 4:5 151:: l x410 9:510 900 59.2 4.0 4.8 4.4 12.4 1 84.8 93.5 925 00.8 i 3.5 4.1 4.5 14.5 i 87.4 94.5 l 1/10 1 1 s75 54.5 I 1.7 5.2 1. 4.0 11.1 80.1 92.1 Promoted Catalyst: H 7

388 33:? 3"? t it 31;; 1 iii Q. 22:? 32:3 4?:3 850 59.0 5:4 5 415 3.2 .6 05.0 1 s31; 91.7 10.7 550 53.0 4.7 3.4 1.5 1 as 52.7 i 75.4 92.5 sas 850 54.0 t 4.3 i 4.7 3.4 1 10.0 58.3 t 70.4 92.6 70.4 815 04.0 1 5.0 1 4.0 as 13.; .19.1 1 s99 92 s 1 7 .0 1 10/1/1 2575 59.5 4.0 E 4.2 l 5.0 V 12.5 04.1 1 84.4 i 92.5 10.0

It is apparent from the data that the promoted cataamount to furnish 1% manganese on the catalyst, calculyst is quite superior to the base catalyst, although the iatedasmanganese from Mn O difference is not as marked as when a fixed bed is used. This catalyst was used to convert propylene and am- The bismuth and boron promoted catalyst was next monia to acrylonitrile, using the apparatus and reaction employed in fixedbed form for the conversion of propyl- 3;, conditions of Example I, in comparison with the base ene to acrolein. During the reaction the reactor was maincatalyst as a control. The results are graphed in FIGURE tained at a temperature of 825 F. at atmospheric pres- 3 as the percent conversion to acrylonitrile versus temsure. The contact time with the catalyst was approxiperature. mately one second. The feed molar ratios were air/H O/ The data show that at the optimum temperature of propylene/nitrogen 5/6/1/32. Approximately 58% of the 850870 F., the total conversion using the catalyst of propylene feed was converted to acrolein and about 29% the invention is 91.2%, of which 68% is acrylonitrile, of the propylene was unreacted. This unreacted material 9.1% acetonitrile, and the remainder carbon dioxide and could be recycled. The remainder of the product consisted hydrogen cyanide. The total useful yield is 85.3%. In this of carbon oxides, minor amounts of low molecular weight case, the improvement over the base catalyst is not so carbonylic compounds, and organic acids. great as when bismuth alane is used, but since manganese is much less costly than bismuth, the reduction can be more than outweighed by the economics in commercial use.

Example IV A group of catalysts were prepared, promoted by the addition of 0.5% boron, in accordance wit hExample II, and using the base catalyst of Example I, with the amount of bismuth added varying from to 10%, the procedure of Example I being used, with the content of bismuth nitrate in the solution being varied proportionately. The purpose was to elucidate the proportions of bismuth at which the enhanced catalytic eifect is observed.

The catalysts were used to convert propylene and ammonia to acrylonitrile using the apparatus and reaction conditions of Example I, and a reaction temperature of 860-870 F., the optimum range. The results obtained are given in FIGURE 4, graphing the percent conversion to acrylonitrile against the percent bismuth on the base catalyst, the percent boron being constant at 0.5%.

The data show that the best enhanced catalytic efiect is observed at from about to about bismuth oxide, calculated as bismuth.

Example V Example I was repeated, to prepare a group of catalysts promoted by 5% bismuth oxide, calculated as bismuth, with the amount of boron being varied from 0% to 5% by varying proportionately the amount of boric acid in the treating solution. The base catalyst of Example I was employed for the impregnation. The purpose was to elucidate the proportions of boron at which the catalytic effect is observed at this amount of bismuth.

The catalysts were used to convert propylene and ammonia to acrylonitrile, using the apparatus of Example I, and a reaction temperature of 860870 F., the optimum range. The results obtained are graphed in FIGURE 5 as percent acrylonitrile against percent boron oxide, calculated as boron.

The data show that the enhanced catalytic elfect is observed at amounts of boron up to about 5%.

Example VI A bismuth silicomolybdate catalyst was prepared following the procedure given in Example I, except that no phosphoric acid was added to the base catalyst slurry. This catalyst was then impregnated with bismuth nitrate and boric acid solution, as described in Example I, and the resulting catalyst used in the oxidation of propylene as in Example I, in comparison with the base catalyst. The promoted catalyst gave an increase of approximately 10% in the conversion of propylene to acrylonitrile, as compared to the base catalyst.

Each of the above examples utilizes the boron and bismuth-promoted catalyst of the invention in comparison against the base catalyst in the oxidation of olefins to oxygenated hydrocarbons, e.g., propylene to acrylonitrile. It will be understood that the promotional effect is also evidenced in the oxidative dehydrogenation of olefins to diolefins, such as butene to butadiene, and amylenes to isoprene, as described in US. Patent No. 2,991,320 to Hearne and Furman, patented July 4, 1961.

All percentages in the specification and claims are by weight, in the case of the catalyst composition, and by volume in the case of gases.

We claim:

1. The process for the manufacture of acrylonitrile and methacrylonitrile from propylene and isobutylene, respectively, which comprises the step of contacting in the vapor phase at a temperature within the range from about 550 to about 1000 F. at which acrylonitrile and methacrylonitrile formation proceeds a mixture of ammonia, an olefin select-ed from the group consisting of propylene and isobutylene and oxygen in a molar ratio of olefin to ammonia of about 1:1 and a molar ratio of olefin to oxygen of from 1:1 to 1:2, with a catalyst composition consisting essentially of oxides of bismuth and molybdenum as the essential catalytic ingredients, the bismuth oxide being present in an amount to furnish a bismuth to molybdenum Bi:Mo atomic ratio of above 1:3, promoted by a mixture of oxides of boron and bismuth in the proportion of about 0.5 to about 1%, calculated as boron, and about 5 to about 10%, calculated as bismuth.

2. A process in accordance with claim 1, in which the olefin is propylene.

3. A process in accordance with claim 1, in which the catalyst composition also includes phosphorus in an amount unto about 5% by weight.

4. A process in accordance with claim 1, in which the catalyst composition includes manganese oxide as a promoter in an amount up to about one-third the weight of the bismuth oxide promoter.

5. A process in accordance with claim 1, in which the catalyst composition also includes silica, the silica being present in an amount from about 25 to about by weight of the catalyst.

6. A process in accordance with claim 5, in which the catalyst composition also includes phosphorus in an amount up to about 5% by weight.

References Cited UNITED STATES PATENTS JOSEPH P. BRUST, Primary Examiner. 

1. THE PROCESS FOR THE MANUFACTURE OF ACRYLONITRILE AND METHACRYLONITRILE FROM PROPYLENE AND ISOBUTYLENE, RESPECTIVELY, WHICH COMPRISES THE STEP OF CONTACTING IN THE VAPOR PHASE AT A TEMPERATURE WITHIN THE RANGE FROM ABOUT 550 TO ABOUT 1000* F. AT WHICH ACRYLONITRILE AND METHACRYLONITRILE FORMATION PROCEEDS A MIXTURE OF AMMONIA, AN OLEFIN SELECTED FROM THE GROUP CONSISTING OF PROPYLENE AND ISOBUTYLENE AND OXYGEN IN A MOLAR RATIO OF OLEFIN TO AMMONIA OF ABOUT 1:1 TO 1:2, WITH A CATALYST COMPOSITION CONSISTING ESSENTIALLY OF OXIDES OF BISMUTH AND MOLYBDENUM AS THE ESSENTIAL CATALYSTIC INGREDIENTS, THE BISMUTH OXIDE BEING PRESENT IN AN AMOUNT TO FURNISH A BIS MUTH TO MOLYBDENUM BI:MO ATOMIC RATIO OF ABOVE 1:3, PROMOTED BY A MIXTURE OF OXIDES OF BORON AND BISMUTH IN THE PROPORTION OF ABOUT 0.5 TO ABOUT 1%, CALCULATED AS BORON, AND ABOUT 5 TO ABOUT 10%, CALCULATED AS BISMUTH. 